JP2019501304A - Bicomponent filament - Google Patents

Abstract

A first region comprising an ethylene-based polymer, a second region comprising a propylene-based polymer, (1) a crystalline ethylene-based polymer, (2) a crystalline alpha-olefin-based polymer, and (3) a crystalline ethylene block And a compatibilizer comprising a crystalline block composite having a block copolymer having a crystalline alpha-olefin block, wherein the crystalline ethylene block is essentially a crystalline ethylene-based polymer. And the crystalline alpha-olefin block is essentially the same composition as the crystalline alpha-olefin-based polymer, and the compatibilizer is in at least one of the first region or the second region. Bicomponent filament present.

Description

  The present disclosure relates to bicomponent filaments, and in particular to bicomponent filaments for use in nonwovens.

  Nonwoven fabric (NW) is a fabric-like material made from filaments that are bundled through different bonding techniques. Nonwoven fabrics may be used in disposable absorbent articles such as diapers, wipes, sanitary products, and adult incontinence products.

  The nonwoven may include polypropylene (PP) due to its excellent processing properties in the spunmelt process, as well as its contribution to the mechanical performance of the product. One of the major disadvantages of nonwoven products containing polypropylene is the lack of flexibility. Flexibility can be addressed by introducing polyethylene (PE) into the nonwoven. Polyethylene can provide flexibility and drapeability, and polypropylene can contribute to the overall mechanical performance, but the loss of nonwoven wear resistance can occur especially as the fabric ages. There is.

  As a result, it is desirable to produce nonwovens from polymer blends of polyethylene and polypropylene having improved wear resistance.

  Disclosed herein is a bicomponent filament. The bicomponent filament comprises a first region comprising an ethylene polymer, a second region comprising a propylene polymer, (1) a crystalline ethylene polymer, (2) a crystalline alpha-olefin polymer, and (3 ) A compatibilizer comprising a crystalline block composite having a crystalline ethylene block and a block copolymer having a crystalline alpha-olefin block, wherein the crystalline ethylene block is essentially the same composition as the crystalline ethylene-based polymer The crystalline alpha-olefin block is essentially the same composition as the crystalline alpha-olefin-based polymer and the compatibilizer is present in at least one of the first region or the second region.

  Also disclosed herein is a method of making a bicomponent filament. The method comprises blending a composition comprising an ethylene-based polymer, a propylene-based polymer, and a compatibilizer, wherein the compatibilizer is (1) a crystalline ethylene-based polymer, (2) a crystalline alpha-olefin-based polymer. And (3) a crystalline block composite having a block copolymer having a crystalline ethylene block and a crystalline alpha-olefin block, wherein the crystalline ethylene block is essentially the same composition as the crystalline ethylene-based polymer; The crystalline alpha-olefin block is essentially the same composition as the crystalline alpha-olefin-based polymer, blending, and extruding the composition to form a bicomponent filament, the bicomponent filament comprising: A first region comprising an ethylene-based polymer and a first region comprising a propylene-based polymer; It comprises regions, compatibilizer, and a to be present in at least one of the first region or the second region to form.

  Further disclosed herein is a nonwoven fabric. The nonwoven fabric includes a first region containing an ethylene-based polymer, a second region containing a propylene-based polymer, (1) a crystalline ethylene-based polymer, (2) a crystalline alpha-olefin-based polymer, and (3) a crystal A bicomponent filament comprising a crystalline block comprising a crystalline ethylene block and a block copolymer having a crystalline alpha-olefin block, wherein the crystalline ethylene block essentially comprises a crystalline ethylene-based polymer The same composition, the crystalline alpha-olefin block is essentially the same composition as the crystalline alpha-olefin-based polymer, and the compatibilizer is present in at least one of the first region or the second region Formed from bicomponent filaments.

  Further disclosed herein is a method of manufacturing a nonwoven fabric. The method provides two or more bicomponent filaments, each bicomponent filament comprising a first region comprising an ethylene-based polymer and a second region comprising a propylene-based polymer; (1) A compatibilizer comprising a crystalline ethylene-based polymer, (2) a crystalline alpha-olefin-based polymer, and (3) a crystalline block complex having a block copolymer having a crystalline ethylene block and a crystalline alpha-olefin block. The crystalline ethylene block is essentially the same composition as the crystalline ethylene-based polymer, the crystalline alpha-olefin block is essentially the same composition as the crystalline alpha-olefin polymer, and the compatibilizer is Providing in at least one of the one region or the second region and providing two or more duplicates And the filament is coupled together, and forming a non-woven fabric.

  Additional features and advantages of the embodiments will be set forth in the following detailed description of the invention, and to some extent will be readily apparent to those skilled in the art from the description, or the following detailed description of the embodiments for implementing the invention, It is recognized by implementing the embodiments described herein, including the claims. Both the foregoing and following description are intended to describe various embodiments and to provide an overview or framework for understanding the nature and characteristics of the claimed subject matter. And should be understood to serve to explain the operation.

  Here, bicomponent filament embodiments, sanitary absorbent articles such as bicomponent filaments that may be used to produce nonwovens for use in diapers, wipes, sanitary products, and adult incontinence products The manufacturing method is referred to in detail. However, it should be noted that this is only an illustrative implementation of the embodiments disclosed herein. The embodiments can be applied to other technologies that are susceptible to the same problems as described above. For example, non-woven fabrics comprising the bicomponent filaments described herein are used to produce face masks, surgical gowns, isolation gowns, surgical drapes and covers, surgical caps, tissues, bandages, and wound dressings These are clearly within the scope of this embodiment. The terms “fiber” and “filament” are used interchangeably herein.

Bicomponent filaments In embodiments herein, the bicomponent filaments comprise a first region comprising an ethylene-based polymer, a second region comprising a propylene-based polymer, and at least one of the first region or the second region. Including a compatibilizer in one.

First region The first region includes an ethylene-based polymer. In some embodiments herein, the first region of the bicomponent filaments is greater than 50 to 99, such as 55 to 99, 75 to 75, based on the total weight of polymer present in the first region. 99, 80-99, 85-99, 50-95, 75-95, 50-90, 75-90 weight percent ethylene-based polymer may be included.

  The ethylene-based polymer is a unit derived from (a) 100 wt% or less, such as at least 70 wt%, or at least 80 wt%, or at least 90 wt%, or at least 92 wt%, or at least 95 wt% ethylene And (b) less than 30%, such as less than 25%, or less than 20%, or less than 10%, or less than 8%, or less than 5% by weight of one or more alpha-olefin comonomers. Includes derived units. As used herein, “ethylene-based polymer” refers to a polymer containing greater than 50 mole percent polymerized ethylene monomer (based on the total amount of polymerizable monomers) and optionally containing at least one comonomer. May be.

  In embodiments herein where the ethylene-based polymer comprises at least one alpha-olefin comonomer, the alpha-olefin comonomer has no more than 20 carbon atoms. For example, the alpha-olefin comonomer may have 3 to 10 carbon atoms, or 3 to 8 carbon atoms. Exemplary alpha-olefin comonomers include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. However, it is not limited to these. The one or more alpha-olefin comonomers are, for example, selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively from the group consisting of 1-hexene and 1-octene. Also good. In embodiments herein, the ethylene-based polymer may or may not be a homopolymer, copolymer, or interpolymer.

  The ethylene-based polymer may be any type of reactor or reactor configuration known in the art, such as a fluidized bed gas phase reactor, loop reactor, stirred tank reactor, parallel, series batch reactor, and / or Or any combination thereof can be used to make through a gas phase, solution phase, or slurry polymerization process, or a combination thereof. In some embodiments, a gas or solution reactor is used. Suitable ethylene-based polymers are described in WO 2005/111291 A1 or US Pat. S. It may be produced according to the process described on pages 15-17 and 20-22 in 2014/0248811. The catalysts used to make the ethylene-based polymers described herein may include Ziegler-Natta, metallocene, constrained geometry, single site catalysts, or combinations thereof. For example, the ethylene-based polymer may include LLDPE, for example, znLLDPE, which refers to linear polyethylene made using a Ziegler-Natta catalyst, linear polyethylene made using a Ziegler-Natta catalyst, It may also be mLLDPE which refers to uLLDPE or “ultra-linear low density polyethylene” or LLDPE made using metallocene or constrained geometry catalyzed polyethylene. Examples of suitable ethylene-based polymers include ASPUN ™ 6850 or ASPUN ™ 6000 available from The Dow Chemical Company, 100-ZA25 available from Ineos Olefins and Polymers Europe, and Saudi Basic Industries Mention may be made of the possible M200056 and MG9601S available from Borealis AG.

  In some embodiments, the ethylene-based polymer comprises (a) polymerizing ethylene and optionally one or more α-olefins in the presence of the first catalyst to produce a first reactor or a multi-part reactor. Forming a semi-crystalline ethylene-based polymer in the first portion; and (b) newly fed ethylene in the presence of a second catalyst comprising an organometallic catalyst and optionally one or more α-olefins. And thereby forming an ethylene-based polymer composition in at least one other reactor or a later portion of the multi-part reactor. Additional exemplary solution and gas phase polymerization processes are described in U.S. Pat. S. 2014/024881 can be found.

  In embodiments herein, the ethylene-based polymer may have a density of 0.920 to 0.965 g / cc. All individual values and subranges are included and disclosed herein. For example, in some embodiments, the ethylene-based polymer has a lower limit of 0.920, 0.925, 0.930, or 0.935 g / cc to 0.945, 0.950, 0.955, 0.960. Or a density up to an upper limit of 0.965 g / cc. In one exemplary embodiment, the ethylene-based polymer may have a density from 0.930 to 0.960 g / cc. In another exemplary embodiment, the ethylene-based polymer may have a density of 0.935 to 0.955 g / cc.

  In embodiments herein, the ethylene-based polymer may have a melt index, I2, of 0.5 to 150 g / 10 min. All individual values and subranges are included and disclosed herein. For example, in some embodiments, the ethylene-based polymer is 1.0, 2.0, 4.0, 5.0, 7.5, 10.0, 12.0, 14.0, or 15.0 g. It may have a melt index, I2, from a lower limit of / 10 minutes to an upper limit of 20, 23, 25, 28, 30, 35, 40, 50, 75, 100, 125, or 150 g / 10 minutes. In one exemplary embodiment, the ethylene-based polymer may have a melt index, I2, of 5-80 g / 10 minutes, 5-50 g / 10 minutes, or 10-50 g / 10 minutes. In another exemplary embodiment, the ethylene-based polymer may have a melt index, I2, of 5 to 35 g / 10 minutes. In a further exemplary embodiment, the ethylene-based polymer may have a melt index, I2, of 15-35 g / 10 min.

  In the embodiments herein, the ethylene-based polymer may have a molecular weight distribution (Mw / Mn) in the range of 2-4. All individual values and subranges are included and disclosed herein. For example, in some embodiments, the ethylene-based polymer has a molecular weight distribution (Mw / Mn) in the range of 2.2-4, 2.5-4, 2.8-4, or 3-4. Also good.

Ethylene-based polymers are additives such as antistatic agents, color enhancers, dyes, lubricants, fillers such as TiO ₂ or CaCO ₃ , opacifiers, nucleating agents, processing aids, pigments, primary antioxidants. , Secondary antioxidants, processing aids, UV stabilizers, antiblocking agents, slip agents, tackifiers, flame retardants, antibacterial agents, odor reducing agents, antifungal agents, and combinations thereof . One or more additives may be included in the ethylene-based polymer at a level typically used in the art to achieve their desired purpose. In some examples, the one or more additives are 0-10% by weight of the ethylene-based polymer, 0-5% by weight of the ethylene-based polymer, 0.001-5% by weight of the ethylene-based polymer, It is included in amounts ranging from 0.001 to 3% by weight, 0.05 to 3% by weight of the ethylene-based polymer, or 0.05 to 2% by weight of the ethylene-based polymer.

Second region The first region includes a propylene-based polymer. As used herein, “propylene-based polymer” refers to a polymer containing greater than 50 mole percent polymerized propylene monomer (based on the total amount of polymerizable monomers), and optionally contains at least one comonomer. May be. In some embodiments herein, the second region of the bicomponent filament is greater than 50 to 99, such as 55 to 99, 75 to 75, based on the total weight of polymer present in the second region. 99, 80-99, 85-99, 50-95, 75-95, 50-90, 75-90 weight percent propylene-based polymer may be included.

  In embodiments herein, the propylene-based polymer is a propylene homopolymer, a propylene copolymer, or a combination thereof. The polypropylene homopolymer may be isotactic, atactic or syndiotactic. In some embodiments, the propylene-based polymer is an isotactic polypropylene homopolymer. In other embodiments, the propylene-based polymer is a propylene / olefin copolymer. The propylene / olefin copolymer may be random or block. The propylene / olefin copolymer is derived from (a) up to 100 wt% propylene, for example at least 70 wt%, or at least 80 wt%, or at least 90 wt%, or at least 92 wt%, or at least 95 wt% And (b) one or more alpha-olefin comonomers less than 30% by weight, such as less than 25% by weight, or less than 20% by weight, or less than 10% by weight, or less than 8% by weight, or less than 5% by weight. Includes units derived from. In further embodiments, the propylene-based polymer may be a combination of one or more propylene homopolymers, one or more propylene copolymers, or a combination of one or more propylene homopolymers and one or more propylene copolymers.

  In embodiments herein where the propylene-based polymer comprises at least one alpha-olefin comonomer, the alpha-olefin comonomer has no more than 20 carbon atoms. For example, the alpha-olefin comonomer may have 3 to 10 carbon atoms, or 3 to 8 carbon atoms. Exemplary alpha-olefin comonomers include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. However, it is not limited to these. The one or more alpha-olefin comonomers may be selected, for example, from the group consisting of ethylene, 1-butene, 1-hexene, and 1-octene, or alternatively from the group consisting of ethylene. In embodiments herein, the propylene-based polymer may or may not be a homopolymer, copolymer, or interpolymer.

  Propylene-based polymers can be made using any method for polymerizing propylene and optionally one comonomer. For example, the gas phase, bulk or slurry phase, solution polymerization, or any combination thereof can be used. The polymerization can be a one-stage or two-stage or multi-stage polymerization process performed in at least one polymerization reactor. In the case of two or multi-stage processes, different combinations can be used, for example gas phase-gas phase, slurry phase-slurry phase, slurry phase-gas phase process. Suitable catalysts can include Ziegler-Natta catalysts, single site catalysts (metallocene or constrained geometry), or nonmetallocene, metal-centered, heteroaryl ligand catalysts, or combinations thereof. Exemplary propylene-based polymers include metallocene polypropylene, such as ACHIEVE ™ 3584 available from the Exxon Mobile Corporation, and LUMICENE ™ MR 2001 available from Total Research & Technology Floyy, and Ziegler-Natta polypropylene. For example, HG475FB available from Borealis AG, Lyondell Basell Industries Holdings, B .; V. May include MOPLEN ™ HP2814 available from Sabic 518A available from Saudi Basic Industries Corporation.

  In embodiments herein, the propylene-based polymer has a melt flow rate (MFR) of 5-100 g / 10 min as determined according to ASTM D 1238 at 230 ° C. and 2.16 kilograms. All individual values and subranges from 0.5 g / 10 min to 100 g / 10 min are included and disclosed herein. For example, in some embodiments, the propylene-based polymer is 5 to 85 g / 10 minutes, 10 to 80 g / 10 minutes, 10 to 75 g / 10 minutes, 10 to 50 g / 10 minutes, 15 to 45 g / 10 minutes, or It has a melt flow rate of 20 g / 10 min to 40 g / 10 min. In embodiments herein, the propylene-based polymer may have a density of 0.900 to 0.910 g / cc, or 0.900 to 0.905 g / cc. The density may be determined according to ASTM D-792.

Propylene polymers are additives such as antistatic agents, color enhancers, dyes, lubricants, fillers such as TiO ₂ or CaCO ₃ , opacifiers, nucleating agents, processing aids, pigments, primary antioxidants. , Secondary antioxidants, processing aids, UV stabilizers, antiblocking agents, slip agents, tackifiers, flame retardants, antibacterial agents, odor reducing agents, antifungal agents, and combinations thereof . One or more additives may be included in the propylene-based polymer at levels typically used in the art to achieve their desired purpose. In some examples, the one or more additives are 0-10% by weight of the propylene-based polymer, 0-5% by weight of the propylene-based polymer, 0.001-5% by weight of the propylene-based polymer, It is included in amounts ranging from 0.001 to 3% by weight, 0.05 to 3% by weight of the propylene-based polymer, or 0.05 to 2% by weight of the propylene-based polymer.

Compatibilizer In embodiments herein, the first region and the second region are compatible with each other by using a compatibilizer. Without being limited by theory, due to the incompatibility between polyethylene and polypropylene, phase separation over time occurs and the polyethylene-polypropylene interface (ie, the first region-second region interface). It is thought that delamination may occur in the case. Thereby, nonwoven fabric abrasion resistance may fall. Use of a compatibilizer in at least one of the first region or the second region can reduce phase separation over time at the polyethylene-polypropylene interface (first region-second region interface); Thereby, it is believed to provide improved nonwoven wear resistance. It is believed that the compatibilizer migrates to the interface between the first region and the second region, causing compatibilization between the two regions.

  In embodiments herein, the compatibilizer is a crystalline block composite. The crystalline block composite comprises (1) crystalline ethylene-based polymer (CEP), (2) crystalline alpha-olefin-based polymer (CAOP), and (3) crystalline ethylene block (CEB) and crystalline alpha-olefin. A block copolymer having a block (CAOB), the crystalline ethylene block is essentially the same composition as the crystalline ethylene-based polymer, and the crystalline alpha-olefin block is essentially the same as the crystalline alpha-olefin-based polymer. The same composition. The crystalline ethylene-based polymer (CEP) can have an ethylene content greater than 90 mol%. The compositional split between the amount of CEP and the amount of CAOP is essentially the same as between the corresponding blocks in the block copolymer. The alpha-olefin content of CAOP and CAOB may be greater than 90 mol%. In an exemplary embodiment, the alpha-olefin is propylene. For example, CAOB and CEB may be iPP-EP (isotactic polypropylene and ethylene-propylene) diblock copolymers.

The crystalline block composite (CBC) has a crystalline ethylene-based polymer (CEP), a crystalline alpha-olefin-based polymer (CAOP), and a crystalline ethylene block (CEB) and a crystalline alpha-olefin block (CAOB). Including block copolymers, CEB is essentially the same composition as CEP, and CAOB is essentially the same composition as CAOP. Alpha-olefins can be referred to as comonomers, the amount of which constitutes the comonomer content. In the crystalline block composite, the alpha-olefin is at least one selected from the group of C _3-10 α-olefins (which may be, for example, propylene and / or butylene). CAOP and CAOB may have an alpha-olefin content greater than 90 mol%. CEB includes units derived from more than 90 mol% ethylene (ie, ethylene content), and any remaining is at least one selected from the group of C _3-10 α-olefins as a comonomer. (Less than 10 mol%, less than 7 mol%, less than 5 mol%, less than 3 mol%, etc.).

In an exemplary embodiment, the CAOP comprises units derived from propylene, eg, greater than 90 mol% propylene, and any remaining is selected from the group of C _4-10 α-olefins as ethylene and / or comonomers. May be at least one (less than 10 mol%, less than 7 mol%, less than 5 mol%, less than 4 mol%, less than 4 mol%, etc.). When CAOB contains propylene, it may further contain ethylene as a comonomer, like CAOP. Further, CEB and CEP may contain propylene as a comonomer. The compositional split between the amount of CEP and the amount of CAOP is essentially the same as between the corresponding blocks in the block copolymer. CEB and CAOB may be referred to as hard (crystalline) segments / blocks.

In an exemplary embodiment, CAOB is present in an amount greater than 93 mole%, greater than 95 mole%, and / or greater than 96 mole% of a monomer (such as propylene) that is one of the C _3-10 α-olefins. Refers to a highly crystalline block of polymerized alpha olefin units present. In other words, the comonomer content (eg, ethylene content) in CAOB is less than 7 mol%, less than 5 mol%, and / or less than 4 mol%. A CAOB having propylene crystallinity may have a corresponding melting point that is 80 ° C. or higher, 100 ° C. or higher, 115 ° C. or higher, and / or 120 ° C. or higher. In an exemplary embodiment, CEB refers to a block of polymerized ethylene units having a comonomer content (such as propylene) of 7 mol% or less, 0 mol% to 5 mol%, and / or 0 mol% to 3 mol%. . In an exemplary embodiment, the CAOB includes all or substantially all propylene units. Such CEB may have a corresponding melting point that is 75 ° C. or higher, 90 ° C. or higher, and / or 100 ° C. or higher.

In exemplary embodiments, the crystalline block composite is 40 wt% to 70 wt% (e.g., 40 wt% to 65 wt%, 45 wt% to 65 wt%, based on the total weight of the crystalline block composite). %, 45 wt% to 60 wt%, 50 wt% to 55 wt%, etc.). The remainder of the total weight of the crystalline block complex may be constituted by units derived from at least one C _3-10 α-olefin (referring to comonomer content). For example, the remainder of the total weight may consist of units derived from propylene.

  The crystalline block composite comprises 0.5 wt% to 95.0 wt% CEP, 0.5 wt% to 95.0 wt% CAOP, and 5.0 wt% to 99.0 wt% crystalline. A block complex may be included. For example, the crystalline block composite may comprise 5.0 wt% to 80.0 wt% CEP, 5.0 wt% to 80.0 wt% CAOP, and 20.0 wt% to 90.0 wt%. A crystalline block complex may be included. The weight percent is based on the total weight of the crystalline block complex. The sum of the weight percentages of CEP, CAOP, and crystalline block complex is equal to 100%. Exemplary measurements of the relative amount of crystalline block complex are described in US Pat. Nos. 8,785,554, 8,822,598, and 8,822,599, as follows: It is referred to as the crystalline block complex index (CBCI). The CBCI for the crystalline block composite is greater than 0 and less than 1.0. For example, CBCI is 0.20-0.99, 0.30-0.99, 0.40-0.99, 0.40-0.90, 0.40-0.85, 0.50-0 .80, and / or 0.55-0.75.

  The crystalline block complex has a Tm greater than 90 ° C. (eg, for both the first and second peaks), a Tm greater than 100 ° C. (eg, both the first and second peaks). And / or greater than 120 ° C. (eg, for both the first peak and the second peak). For example, Tm ranges from 100 ° C to 250 ° C, 110 ° C to 220 ° C, and / or 115 ° C to 220 ° C. According to exemplary embodiments, the crystalline block composite has a second peak Tm and 110 ° C. to 150 ° C. in the range of 100 ° C. to 130 ° C. (eg, 100 ° C. to 120 ° C., 100 ° C. to 110 ° C., etc.). The first peak Tm is exhibited in a range of ° C (for example, 110 ° C to 140 ° C, 115 ° C to 130 ° C, 115 ° C to 125 ° C, etc.), and the second peak Tm is less than the first peak Tm.

  Crystalline block composites may be distinguished from conventional random copolymers, physical blends of polymers, and block copolymers prepared via sequential monomer addition. Crystalline block composites are random copolymers, as well as properties such as crystalline block composite index, better tensile strength, improved fracture strength, more precise morphology, improved optical components, and / or low temperatures. May be distinguished from physical blends with greater impact strength. Crystalline block composites may be distinguished from block copolymers prepared by sequential monomer addition by molecular weight distribution, rheology, shear thinning, rheological ratio, and block polydispersity. A unique feature of crystalline block complexes is that they cannot be fractionated by conventional means by solvent or temperature, such as xylene fractionation, solvent / non-solvent or temperature rising elution fractionation, or crystal elution fractionation. Yes, because the individual blocks of the block copolymer are crystalline.

When produced in a continuous process, the crystalline block composite desirably has a PDI of 1.7-15 (eg, 1.8-10, 2.0-5, and / or 2.5-4.8). Own. Exemplary crystalline block composites are described, for example, in U.S. Patent Application Publication Nos. 2011-0313106, 2011-0313107, and 2011-0313108, all published December 22, 2011. Which are incorporated herein by reference with respect to the description of the crystalline block complex, the process of making the crystalline block complex, and the method of analyzing the crystalline block complex. In an exemplary embodiment, the crystalline block composite has a weight average molecular weight of 5.0 or less, 3.0 to 4.8, and / or 3.0 to 4.0 number average molecular weight (M _w / M _n ) may have a molecular weight distribution (MWD), defined as the value divided by _n ).

  The crystalline block composite polymer comprises contacting an addition polymerizable monomer or mixture of monomers under addition polymerization conditions with a composition comprising at least one addition polymerization catalyst, at least one cocatalyst, and a chain transfer agent. May be prepared by a process, the process being distinguished in two or more reactors operating under steady state polymerization conditions or in two or more zones of a reactor operating under plug flow polymerization conditions. Forming at least part of the growing polymer chain under different process conditions. The term “shuttling agent” refers to a compound or mixture of compounds that can cause polymer exchange between at least two active catalytic sites under polymerization conditions. That is, migration of the polymer fragment occurs between one or more of the active catalytic sites. In contrast to shuttling agents, “chain transfer agents” cause polymer chain growth to stop, resulting in a one-time transfer of the growing polymer from the catalyst to the transfer agent. In a preferred embodiment, the block complex and the crystalline block complex comprise a fraction of the block polymer having the most probable distribution of block lengths.

  Suitable processes useful for the production of crystalline block composites can be found, for example, in US Patent Application Publication No. 2008/0269412 published Oct. 30, 2008. In particular, the polymerization is desirably carried out as a continuous polymerization, preferably as a continuous solution polymerization, where the catalyst components, monomers, and optionally the solvent, adjuvant, scavenger, and polymerization aid are in one or more reactors. Alternatively, it is continuously fed to the zone from which the polymer product is continuously removed. Within the scope of the terms “continuous” and “continuously” as used in this context are intermittent additions of reactants and removal of products at slight regular or irregular intervals, Thereby, those processes in which the overall process is substantially continuous over time. The chain shuttling agent is in the first reactor or zone, just before the outlet of the first reactor or the outlet of the first reactor, or the first reactor or zone and the second reactor or zone. Or at any point during the polymerization, including between any subsequent reactors or zones. Due to monomer, temperature, pressure differences, or other differences in the polymerization conditions between at least two of the reactors or zones connected in series, comonomer content, crystallinity, density, stereoregularity, positional rules Polymer segments of different compositions, such as sex, or other chemical or physical differences within the same molecule, are formed in different reactors or zones. The size of each segment or block is determined by the continuous polymer reaction conditions and is preferably the most likely polymer size distribution.

  For example, when producing a block copolymer having a crystalline ethylene block (CEB) and a crystalline alpha-olefin block (CAOB) in two reactors or zones, the CEB in the first reactor or zone, and the second reaction It is possible to produce CAOB in the reactor or zone, or CAOB in the first reactor or zone, and CEB in the second reactor or zone. It may be more advantageous to produce CEB in the first reactor or zone with the addition of new chain shuttling agent. Increasing ethylene levels in a reactor or zone that produces CEB can result in a much higher molecular weight in that reactor or zone than in a zone or reactor that produces CAOB. The new chain shuttling agent reduces the molecular weight of the polymer in the reactor or zone that produces CEB, which provides a good overall balance between the length of the CEB and CAOB segments.

  When operating reactors or zones in series, it is necessary to maintain a variety of reaction conditions such that one reactor produces CEB and the other reactor produces CAOB. The ethylene carryover from the first reactor (in series) to the second reactor or from the second reactor to the first reactor by the solvent and monomer recycling system is preferably minimized. The There are many possible unit operations to remove this ethylene, but since ethylene is more volatile than higher alpha olefins, one simple method reduces the pressure of the reactor effluent, It is to remove most of the unreacted ethylene through the flash step by producing CEB and removing the ethylene with a flash. A more preferred approach is to take advantage of the very good reactivity of ethylene to higher alpha olefins so that additional unit operations are avoided and the conversion of ethylene over the CEB reactor approaches 100%. For CAOB, the overall monomer conversion across the reactor may be controlled by maintaining alpha-olefin conversion at high levels (90-95%). Exemplary catalysts and catalyst precursors for use between crystalline block composites include, for example, metal complexes disclosed in WO2005 / 090426.

  The crystalline block complex is 10,000 g / mol to 2,500,000 g / mol, 35,000 g / mol to 1,000,000 g / mol, 50,000 g / mol to 300,000 g / mol, and / or You may have a weight average molecular weight (Mw) of 50,000 g / mol-200,000 g / mol. For example, Mw may be 20 kg / mol to 1000 kg / mol, 50 kg / mol to 500 kg / mol, and / or 80 kg / mol to 125 kg / mol.

  The MFR (melt flow rate) of the crystalline block composite is 0.1 to 1000 dg / min (230 ° C./2.16 kg) at 230 ° C. and 2.16 kg when measured according to ASTM D 1238, 1 to It may be 500 dg / min (230 ° C./2.16 kg), 5-100 g / 10 min, 5-50 g / 10 min, or 9-40 g / 10 min.

  The compatibilizer may be present in at least one of the first region or the second region. In some embodiments, the compatibilizer is 1 to less than 50 wt%, 2 to 45 wt%, 2 to 40 wt%, 2 to 35 wt%, based on the total weight of polymer present in the second region. %, 2 to 30%, 5 to 35%, 5 to 30%, 5 to 25%, or 5 to 20% by weight in the first region only. In other embodiments, the compatibilizer is 1 wt% to less than 50 wt%, 2 to 45 wt%, 2 to 40 wt%, 2 to 35, based on the total weight of polymer present in the second region. It is present only in the second region in an amount of wt%, 2-30 wt%, 5-35 wt%, 5-30 wt%, 5-25 wt%, or 5-20 wt%. In a further embodiment, the compatibilizer is 1 wt% to less than 50 wt%, 2 to 45 wt%, 2 to 40 wt% based on the total weight of the polymer present in the first and second regions. In the first region and the second region in amounts of 2 to 35%, 2 to 30%, 5 to 35%, 5 to 30%, 5 to 25%, or 5 to 20% by weight May be present simultaneously.

Bicomponent filaments and non-woven fabrics The bicomponent filaments described herein may be produced by a melt spinning process that includes short fiber spinning (including short spinning and long spinning). In some embodiments, the bicomponent filament is blending a composition comprising an ethylene-based polymer, a propylene-based polymer, and a compatibilizer and extruding the composition to form a bicomponent filament, The component filament includes a first region including an ethylene-based polymer, a second region including a propylene-based polymer, and a compatibilizer is present in at least one of the first region or the second region. It may be produced by doing. Ethylene-based polymers, propylene-based polymers, and compatibilizers have been previously described herein.

  The resulting bicomponent filament cross-section may resemble a variety of different configurations. For example, the first and second regions of the bicomponent filament may be in the form of a sheath / core, tip trefoil, segmented cloth, side-by-side, conjugate, island in sea, or segmented pie May be arranged. In some embodiments, the first region and the second region of the bicomponent filament are sheath / core, tip trefoil, segmented cloth, side-by-side, conjugate, island-in-sea, or segmented. And at least one outer surface of the bicomponent filament comprises an ethylene-based polymer blended with a crystalline block composite compatibilizer.

  In some embodiments, the first region and the second region of the bicomponent filament may each have a sheath-core structure. The sheath layer is disposed on the core and surrounds the peripheral surface of the core. The core to sheath weight ratio may range from 50:50 to 90:10, 60:40 to 90:10, or 65:35 to 90:10. The use of an ethylene-based polymer in the sheath can improve the flexibility or tactile sensation of the nonwoven fabric. Conversely, non-woven fabrics comprising filaments made only from high modulus polymers such as polypropylene homopolymer can provide different tactile sensations and are often considered to be less soft. However, fabrics composed of ethylene-based polymers in the sheath can suffer from reduced abrasion resistance compared to fabrics made only from polypropylene. Tactile sensation is not easily quantified, but can be assessed using a sensory panel. Sensory panelists can be asked to rank the various samples according to attributes such as “smoothness”, “cloth-like”, “stiffness”, and “noise intensity”. A more objective test involves the use of a commercially available device known as “Handle-O-Meter”. “Handle-O-Meter” is a device commercially available from Thwing-Albert Company.

  The bicomponent filaments described herein may be used to form nonwovens. Nonwovens can be produced by various methods generally known in the art, examples of which include, for example, “Introduction to Nonwoven Technologies” by Subra, Subhash and Pourdehymi, Bahnam, 2012, and “Polyolefin: and Medical Applications, "S. C. O. Ugbolue, 2009. As used herein, the terms “nonwoven web” or “nonwoven fabric” or “nonwoven” are used to refer to individual fibers or interleaved but not in a regular repeating manner. It refers to a web having a filament structure.

  The nonwoven web may comprise a single web, such as a spunbond web, a card web, an airlaid web, a spunlace web, or a meltblown web. “Meltblown” refers to melting thermoplastic material as molten yarns or filaments, through a plurality of fine, usually annular mold capillaries, by which the filaments of molten thermoplastic material are thinned to reduce the diameter of the microfiber. Refers to the process of extruding into a stream of high velocity gas (eg, air) that decreases in diameter. The meltblown fibers are then carried by the high velocity gas stream and are deposited on the collecting surface to form a randomly dispersed web of meltblown fibers. “Spunbond” is a method of extruding a molten thermoplastic material as filaments from a capillary tube of an annular spinneret having a diameter of a plurality of fine, usually extruded filaments, and then drawing the fibers onto a substrate. Refers to a process that rapidly decreases by collecting fibers.

Due to the relative advantages and disadvantages associated with the different processes and materials used to make nonwovens, multiple layer composite structures are often used to achieve a better balance of properties. Such structures are often, SMS for SM, 3-layer structure for a two-layer structure consisting of spunbond layers and a meltblown layer or, more generally, such as S _n X _n S _n structure Identified by letters designating the various layers, “X” can independently be a spunbond layer, a carding layer, an airlaid layer, a spunlace layer, or a meltblown layer, where “n” is Although it can be any number, in practice it is generally less than 5. In order to maintain the structural integrity of such a composite structure, the layers must be bonded together. Common methods of bonding include thermal calendar point bonding, adhesive lamination, ultrasonic bonding, and other methods known to those skilled in the art. All of these structures may be used in the present invention.

  In some embodiments, where the nonwoven comprises bicomponent filaments having a core / sheath configuration, and the propylene-based polymer used for the core has a higher melting point than the ethylene-based polymer used for the sheath, the sheath is heat calendered The bonding temperature of the nonwoven fabric in can be lowered. The sheath may also provide other properties to the nonwoven such as flexibility or certain haptic properties, while the core layer may provide other properties such as tensile strength. In addition, since the propylene-based polymer used for the core has a higher melting point than the ethylene-based polymer used for the sheath layer, the propylene-based polymer used for the core does not completely melt / flow and is in the nonwoven fabric. Level integrity and strength can be provided.

  In some embodiments, the nonwoven fabric is also a laminate such as a spunbond layer and several meltblown layers, such as a spunbond / meltblown / spunbond (SMS) laminate, and US Pat. No. 4 to Block et al. No. 5,041,203, US Pat. No. 5,169,706 to Collier et al., US Pat. No. 5,145,727 to Potts et al., US Pat. No. 5,178,931 to Perkins et al., And US to Timmons et al. There may be others disclosed in US Pat. No. 5,188,885, each of which is incorporated by reference in its entirety. The non-woven fabric may be an elastic non-woven fabric composed of an elastic material, or an extensible non-woven fabric such as a spunlace material that is a hydroentangled spun melted non-woven fabric. The nonwoven fabric may be inelastic, but may be extensible or extensible. Such non-elastic nonwovens may be used in elastic laminates by bonding them to an elastic film, but the elastic film shrinks a non-woven gather or packer between the parts where the nonwoven is bonded to the elastic film The elastic film is in a stretched state so as to cause wrinkles in the nonwoven fabric. This laminate live stretch process is described in US Pat. No. 4,720,415. Other means for wrinkling the nonwoven fabric are commercially available, for example, made by Microx. Stretchable but inelastic nonwovens can also be used in elastic laminates by a process described as stepwise stretching. In these processes, the elastic film and the extensible but inelastic nonwoven fabric are joined in an unstretched state. The laminate is then as described in US Pat. Nos. 5,167,897, 4,107,364, 4,209,463, and 4,525,407. Subject to stretching or tension. When tension is released on the web, the nonwoven fabric is permanently deformed in the stretched area and does not return to its original shape, so the elastic laminate is significantly constrained from the nonwoven fabric in the pre-stretched area. Without being stretched, it can be stretched and recovered.

  In some embodiments, a laminate having an SMS structure, i.e., a meltblown nonwoven layer disposed between two spunbond nonwoven layers, may be manufactured for use in a variety of different articles. Spunbond nonwovens include the bicomponent filaments described herein, whereas meltblown nonwovens include monocomponent fibers that can include a propylene-based polymer. The presence of a compatibilizer in the fibers of the spunbond layer promotes adhesion with the propylene-based polymer in the meltblown layer, producing a unique product with a synergistic combination of tensile strength, flexibility, and barrier properties. Is done.

The combination of spunbond and meltblown layers in the laminate can promote improved barrier properties, such as hygiene absorbent products such as diapers, training pants, or leg cuffs in adult incontinence products Important for drape and gown use, or face mask applications. The presence of an ethylene-based polymer in the sheath improves the flexibility or tactile feel of the nonwoven laminate, and the presence of a compatibilizer in the sheath or in the sheath and core allows for improved wear resistance of the spunbond nonwoven. The SMS laminate produced in this way exhibits an optimal combination of flexibility, barrier properties, abrasion resistance, and laminate tensile strength. Multiple spunbond layers and meltblown layers can be bonded in this manner. In other words, a laminate having the structure of (SM) _x (where _x can be any integer greater than or equal to 2) may be manufactured for use. Laminate structures may be made by successively depositing nonwovens: first a spunbond fabric is deposited on a conveyor belt, followed by a meltblown fabric and then another spunbond fabric. These layers may be bonded together by various means including thermal calendar bonding or ultrasonic bonding.

Test Methods A discussion of the methods used herein can also be found, for example, in US Pat. No. 8,822,599, incorporated herein by reference. Test methods include the following:

Density Samples are prepared according to ASTM D-1928. Measurements are made within 1 hour of sample press using ASTM D-792, Method B.

Melt Index Melt index or I ₂ is measured according to ASTM D1238, condition 190 ° C./2.16 kg, and is reported in grams eluted per 10 minutes.

Melt Flow Rate Melt flow rate (MFR) is measured according to ASTM-D1238, condition 230 ° C./2.16 kg. Results are reported in grams / 10 minutes.

Tensile test Tensile test (including elongation at break in machine direction (MD) and cross direction (CD) and tensile strength in machine direction (MD) and cross direction (CD)) is according to DIN EN ISO 29073: 1992-08 To be implemented.

High temperature liquid chromatography (HTLC)
HTLC is performed according to the methods disclosed in US Patent Application Publication No. 2010-0093964 and US Patent Application No. 12 / 643,111 filed December 21, 2009, both of which are hereby incorporated by reference. Embedded in the book. Samples are analyzed by the methodology described below.

  A Waters GPCV2000 high temperature SEC chromatograph was reconstructed to construct an HT-2DLC instrument. Two Shimadzu LC-20AD pumps were connected to the GPCV2000 injector valve by a binary mixer. A first dimension (D1) HPLC column was connected between the injector and a 10-port switch valve (Valco Inc). A second dimension (D2) SEC column was connected between a 10-port valve and LS (Varian Inc.), IR (concentration and composition), RI (refractive index), and IV (intrinsic viscosity) detectors. The RI and IV were GPCV2000 built-in detectors. The IR5 detector was provided by PolymerChar, Valencia, Spain.

  Column: The D1 column was a high temperature Hypercarb graphite column (2.1 x 100 mm) purchased from Thermo Scientific. The D2 column was a PLRapid-H column (10 × 100 mm) purchased from Varian.

  Reagent: HPLC grade trichlorobenzene (TCB) was purchased from Fisher Scientific. 1-decanol and decane were from Aldrich. 2,6-Di-tert-butyl-4-methylphenol (Ionol) was also purchased from Aldrich.

  Sample preparation: 0.01-0.15 g of polyolefin sample was placed in a 10 mL Waters autosampler vial. Thereafter, either 7 mL of 1-decanol or decane containing 200 ppm of ionol was added to the vial. After sparging the sample vial with helium for about 1 minute, the sample vial was placed on a heated shaker set at 160 ° C. Dissolution was performed by shaking the vial at that temperature for 2 hours. The vial was then transferred to an autosampler for injection. Note that the actual volume of the solution was greater than 7 mL due to the thermal expansion of the solvent.

  The HT-2DLC: D1 flow rate was 0.01 mL / min. The mobile phase composition was 100% weak eluent (1-decanol or decane) for the first 10 minutes of the experiment. The composition was then increased to 60% strong eluate (TCB) at 489 minutes. Data was collected for 489 minutes as the duration of the raw chromatogram. The 10-port valve was switched every 3 minutes to obtain 489/3 = 163 SEC chromatogram. After a data acquisition time of 489 minutes, a post-run gradient was used to wash and equilibrate the column for the next run:

Cleaning step:
490 minutes: Flow rate = 0.01 minutes; // Maintain constant flow rate of 0.01 mL / min from 0 to 490 minutes 491 minutes: Flow rate = 0.20 minutes; // Increase flow rate to 0.20 mL / min 492 Minute:% B = 100; // Increase the mobile phase composition to 100% TCB 502 minutes:% B = 100; // Wash column using 2 mL TCB

Equilibrium step:
503 min:% B = 0; // Change the mobile phase composition to 100% 1-decanol or decane 513 min:% B = 0; // Use 2 mL of weak eluent to equilibrate column 514 min : Flow rate = 0.2 mL / min; // Maintain constant flow rate of 0.2 mL / min for 491 to 514 minutes 515 minutes: Flow rate = 0.01 mL / min; // Reduce flow rate to 0.01 mL / min

  After step 8, the flow rate and mobile phase composition were the same as the initial conditions of the operating gradient. The D2 flow rate was 2.51 mL / min. Two 60 μL loops were attached to the 10-port switch valve. 30 μL of the eluate from the D1 column was loaded into the SEC column with each switch of the valve.

  IR, LS15 (light scattering signal at 15 °), LS90 (light scattering signal at 90 °), and IV (intrinsic viscosity) signals were collected by EZChrom through an SS420X analog-to-digital conversion box. Chromatograms were exported in ASCII format and imported into home MATLAB software for data reduction. Use an appropriate calibration curve for the polymer composition and retention capacity of the polymer that is similar in nature to the CAOB and CEB polymers being analyzed. The calibration polymer is narrow in composition (both molecular weight and chemical composition) and must span a reasonable molecular weight range to cover the desired composition during analysis. Analysis of the raw data was calculated as follows, and the first dimension HPLC chromatogram was plotted by plotting the IR signal of all cuts (from the cut's total IR SEC chromatogram) as a function of elution volume. Restructured. The amount of elution of IR vs. D1 was normalized with the total IR signal, and a weight fraction vs. elution amount plot of D1 was obtained. The IR methyl / measurement ratio was obtained from the reconstructed IR measurements and the IR methyl chromatogram. The ratio was converted to composition using a PP wt% (by NMR) versus methyl / measurement calibration curve obtained from a SEC experiment. MW was obtained from reconstructed IR measurements and LS chromatograms. The ratio was converted to MW after calibration of both IR and LS detectors using PE standards.

Differential scanning calorimetry (DSC)
Differential scanning calorimetry is performed on a TA Instruments Q1000 DSC equipped with an RCS cooling accessory and an autosampler. A nitrogen purge gas flow of 50 ml / min is used. The sample is pressed into a thin film, melted in the press at about 230 ° C., and then air cooled to room temperature (25 ° C.). Then about 3-10 mg of material is cut, accurately weighed, and placed in a light aluminum pan (about 50 mg) that is later crimped closed. The thermal behavior of the sample is investigated with the following temperature profile: the sample is heated rapidly to 230 ° C. and held isothermal for 3 minutes to remove previous thermal history. The sample is then cooled to −90 ° C. at a cooling rate of 10 ° C./min and held at −90 ° C. for 3 minutes. The sample is then heated to 230 ° C. at a heating rate of 10 ° C./min. Record the cooling and second heating curve.

¹³ C nuclear magnetic resonance (NMR)
Sample Preparation-The sample was approximately 2.7 g of a 50/50 mixture of tetrachloroethane-d2 / orthodichlorobenzene, 0.025 M in chromium acetylacetonate (relaxation agent), 0.21 g in a 10 mm NMR tube. Prepare by adding to sample. Dissolve and homogenize the sample by heating the tube and its contents to 150 ° C.

  Data Acquisition Parameters—Data is collected using a Bruker 400 MHz spectrometer equipped with a Bruker Dual DUL high temperature CryoProbe. Using 320 transients per data file, 7.3 second pulse repetition delay (6 second delay + 1.3 second acquisition time), 90 degree flip angle, and reverse gate decoupling at a sample temperature of 125 ° C. To get data. Perform all measurements on samples that are not rotated in lock mode. Samples are homogenized just prior to insertion into a heated (130 ° C.) NMR Sample changer and allowed to thermally equilibrate on the probe for 15 minutes prior to data acquisition. The comonomer content in the crystalline block composite polymer can be measured using this technique.

Gel permeation chromatography (GPC)
The gel permeation chromatography system consists of a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220 instrument. The column and carousel compartments operate at 140 ° C. Three Polymer Laboratories 10-micrometer Mixed-B columns are used. The solvent is 1,2,4 trichlorobenzene. Samples are prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent containing 200 ppm butylated hydroxytoluene (BHT). Samples are prepared by agitating lightly for 2 hours at 160 ° C. The injection volume used is 100 microliters and the flow rate is 1.0 ml / min.

Calibration of the GPC column set is based on 21 narrow molecular weight distribution polystyrene standards with molecular weights in the range of 580-8,400,000 placed in six “cocktail” mixtures with at least a decade separation between individual molecular weights. Done. Standards are purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards are prepared at 0.025 grams in 50 milliliters of solvent for molecular weights greater than 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. Dissolve the polystyrene standards at 80 ° C. with gentle agitation for 30 minutes. A narrow standard mixture is run first, in order of decreasing maximum molecular weight components to minimize degradation. The polystyrene standard peak molecular weight is calculated as follows (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): M _{polypropylene} = 0.645 (M _polystyrene ) Is converted to polyethylene molecular weight.

  Polypropylene equivalent molecular weight calculations are performed using Viscotek TriSEC software version 3.0.

Fluff level The fluff level is determined by the Superland 2000 Ink Rub Tester. Polish a 11.0 cm x 4.0 cm piece of non-woven fabric with sand paper according to ISO POR 01 106 so that loose fibers accumulate on top of the laminate (apply cloth sand paper aluminum oxide 320 grit to a weight of 2 pounds, Rubbing 20 cycles at a rate of 42 cycles per minute). Loose fibers are collected using tape and measured gravimetrically. The fuzz level is then determined as the total weight of loose fibers (grams) divided by the laminate sample surface area (44.0 cm ² ).

  These examples were conducted to demonstrate the preparation of bicomponent filaments that can be used in the manufacture of nonwovens. The bicomponent filament has an ethylene-based polymer sheath layer disposed on a core containing a propylene-based polymer.

Crystalline Block Complex Preparation Crystalline block complexes (CBC1 and CBC2) are prepared using two continuous stirred tank reactors (CSTR) connected in series. The first reactor is approximately 12 gallons in volume, while the second reactor is approximately 26 gallons. Each reactor is filled with hydraulic pressure and set to operate under steady state conditions. Monomer, solvent, catalyst, cocatalyst-1, cocatalyst-2, and CSA-1 are flowed to the first reactor according to the process conditions outlined in Table 1. The contents of the first reactor are then flowed through a second reactor in series as described in Table 1 below. Additional catalyst, cocatalyst-1, and cocatalyst-2 are added to the second reactor. Table 2 below shows the analytical characteristics of CBC.

In particular, catalyst-1 ([[rel-2 ′, 2 ′ ″-[(1R, 2R) -1,2-cyclohexanediylbis (methyleneoxy-κO)] bis [3- (9H-carbazole-9- Yl) -5-methyl [1,1′-biphenyl] -2-olato-κO]] (2-)] dimethyl-hafnium) and cocatalyst-1, USP 5,919,983, Ex. 2. Of long-chain trialkylamines (Armeen ™ M2HT available from Akzo-Nobel, Inc.), HCl, and Li [B (C ₆ F ₅ ) ₄ ], substantially as disclosed in US Pat. The mixture of tetrakis (pentafluorophenyl) borate methyldi (C _14-18 alkyl) ammonium salt prepared by is purchased from Boulder Scientific and used without further purification. CSA-1 (diethyl zinc or DEZ) and cocatalyst-2 (modified methylalumoxane (MMAO)) are purchased from Akzo Nobel and used without further purification.

  The solvent for the polymerization reaction is a hydrocarbon mixture (ISOPAR® E) available from the ExxonMobil Chemical Company and is purified through a bed of 13-X molecular sieves prior to use. Referring to Table 1, process conditions for generating CBC2 are shown.

  Calculation of the composition of the crystalline block composite, the weight percent of propylene from each component in the polymer according to Equation 1, sums to the total weight percent of propylene and / or ethylene (of the entire polymer). This mass balance equation can be used to quantify the amount of polypropylene (PP) and polyethylene (PE) present in the block copolymer. This mass balance equation can also be used to quantify the amount of PP and PE in a two-component formulation or extend to a ternary or n-component formulation. In the case of crystalline block composites, the total amount of PP or PE is contained within the blocks and blocks present in the unbound PP and PE polymers.

Where
w _PP = weight fraction of PP in the polymer w _PE = weight fraction of _{PE in the} polymer wt% C3 _PP = weight percentage of propylene in the PP component or block wt% C3 _PE = of propylene in the PE component or block Weight percent.

Note that the total weight percent of propylene (C ₃ ) is preferably measured from C ¹³ NMR or some other composition measurement that represents the total amount of C ₃ present in the entire polymer. The weight% of propylene in the PP block (wt% C _3PP ) is set to 100 or, if known from its DSC melting point, NMR measurements, or other composition estimates, that value can be put in place it can. Similarly, the weight percent of propylene in the PE block (wt% C _3PE ) is set to 100 or, if known from its DSC melting point, NMR measurements, or other composition estimates, that value is in place. Can be put.

  The crystalline block complex index (CBCI) is measured based on the method shown in Table 3 below. In particular, CBCI is based on the assumption that the ratio of CEB to CAOB in the diblock copolymer is the same as the ratio of crystalline ethylene to crystalline alpha-olefin in the total crystalline block composite. Provides an estimate of the amount of block copolymer in the body. This assumption is for these statistical olefin block copolymers based on an understanding of the individual catalyst kinetics and polymerization mechanism to form diblocks via chain transfer catalysis as described herein. It is valid. This CBCI analysis shows that the amount of isolated PP is less than when the polymer is a simple blend of propylene homopolymer (CAOP in this example) and polyethylene (CEP in this example). Thus, the polyethylene fraction contains significant amounts of propylene that are not normally present when the polymer was simply a blend of polypropylene and polyethylene. To account for this “extra propylene”, mass balance calculations are performed to calculate the amount of polypropylene and polyethylene fractions and the weight percent of propylene present in each of the fractions separated by high temperature liquid chromatography (HTLC). CBCI can be estimated. CBCI is calculated based on the following as shown in Table 3:

  Referring to Table 3 above, the crystalline block composite index (CBCI) is first measured by determining the total weight percent of propylene from each component in the polymer according to Equation 1 below, thereby: The total weight percent is obtained as described above with respect to the method for calculating the composition of the crystalline block composite. In particular, the mass balance equation is:

Where
w _PP = weight fraction of PP in the polymer w _PE = weight fraction of _{PE in the} polymer wt% C3 _PP = weight percentage of propylene in the PP component or block wt% C3 _PE = of propylene in the PE component or block Weight percent

For the calculation of the ratio of PP to PE in the crystalline block composite:
Based on Equation 1, the total weight fraction of PP present in the polymer can be calculated using Equation 2 from the total C3 mass balance measured in the polymer. Alternatively, it can be estimated from the mass balance of monomer and comonomer consumption during polymerization. Overall, this represents the amount of PP and PE present in the polymer, whether present in the unbound component or in the diblock copolymer. For conventional blends, the PP and PE weight fractions correspond to the individual amounts of PP and PE polymers present. For crystalline block composites, it is hypothesized that the PP to PE weight fraction ratio also corresponds to the average block ratio between PP and PE present in this statistical block copolymer.

Where
w _PP = weight fraction of PP present throughout the polymer wt% C3 _PP = weight percent of propylene in the PP component or block wt% C3 _PE = weight percent of propylene in the PE component or block

  In order to estimate the amount of block in the crystalline block complex, Equations 3-5 are applied and the amount of isolated PP measured by HTLC analysis is used to determine the amount of polypropylene present in the diblock copolymer. Determine the amount. The amount initially isolated or separated in HTLC analysis represents “unbound PP” and its composition represents the PP hard blocks present in the diblock copolymer. Substituting the total weight% C3 of the total polymer on the left side of Formula 3 as well as the weight fraction of PP (isolated from HTLC) and the weight fraction of PE (isolated by HTLC) into the right side of Formula 3 The weight percent of C3 in the PE fraction can be calculated using equations 4 and 5. The PE fraction is described as a fraction separated from unbound PP and contains diblock and unbound PE. The composition of the isolated PP is assumed to be the same as the weight percentage of propylene in the iPP block described above.

Where
w _PPisolated = weight _{fraction of} PP isolated from HTLC w _PE-fraction = weight _{fraction of} PE separated from HTLC containing diblock and unbound PE wt% C3 _PP = in PP block and unbound PP % Weight of propylene in PP which is also the same amount of propylene present in wt% C3 _PE-fraction = weight percentage of propylene in the _{PE fraction} separated by HTLC wt% C3 _Overall = total weight of propylene in the whole polymer percent

  The amount of weight% C3 in the polyethylene fraction from HTLC is the amount of propylene present in the block copolymer fraction and is greater than the amount present in “unbound polyethylene”. To account for the “additional” propylene present in the polyethylene fraction, the only way to have PP present in this fraction is to link the PP polymer chain to the PE polymer chain (or by HTLC). Isolated in the separated PP fraction). Thus, the PP block remains adsorbed on the PE block until the PE fraction is separated.

  The amount of PP present in the diblock is calculated using Equation 6.

Where
wt% C3 _PE-fraction = weight percent of propylene in the PE fraction separated by HTLC (Equation 4)
wt% C3 _PP = weight percent of propylene in PP component or block (as defined above)
wt% C3 _PE = weight percent of propylene in the PE component or block (as defined above)
w _PP-diblock = weight fraction of PP in diblock separated by PE fraction by HTLC

The amount of diblock present in this PE fraction can be estimated by assuming that the ratio of PP block to PE block is the same as the overall PP to PE ratio present in the overall polymer. For example, if the overall ratio of PP to PE was 1: 1 in the overall polymer, it was assumed that the ratio of PP to PE in the diblock was also 1: 1. Therefore, the weight fraction of the diblock present in the PE fraction is _obtained by multiplying the weight fraction of PP in the diblock ( _wPP-diblock ) by 2. Another way to calculate this is to divide the weight fraction of PP in _diblock ( _wPP-diblock ) by the weight fraction of PP in the entire polymer (Equation 2).

  To further estimate the amount of diblock present in the entire polymer, multiply the estimated amount of diblock in the PE fraction by the weight fraction of the PE fraction measured from HTLC. To estimate the crystalline block composite index, the amount of diblock copolymer is determined by Equation 7. To estimate CBCI, the weight fraction of diblock in the PE fraction calculated using Equation 6 is divided by the total weight fraction of PP (as calculated in Equation 2), then Multiply the weight fraction of the PE fraction. CBCI values can range from 0 to 1, where 1 is equal to 100% diblock and zero is for materials such as conventional blends or random copolymers.

Where
w _PP-diblock = weight fraction of PP in diblock separated by PE fraction by HTLC (Equation 6)
w _PP = weight _fraction of PP in polymer w _PE-fraction = weight _{fraction of} PE separated from HTLC containing diblock and unbound PE (Equation 5)

  For example, an iPP-PE (ie isotactic polypropylene block and propylene-ethylene block) polymer contains a total of 53.3% C3, 10% C3 PE polymer and 99% C3 by weight. When made under conditions such as to produce iPP polymers, the PP and PE weight fractions are each 0.487 to 0.514 (when calculated using Equation 2).

Bicomponent filaments and nonwovens The remainder of the examples relates to materials and methods used in the production of bicomponent filaments. The materials used in the bicomponent filament are shown in Table 4 below.

  Table 5 shows the various fibers produced in the nonwoven fabric for testing. Samples # 1 and # 2 are comparative samples, and samples # 3-10 are samples of the present invention. In Samples # 3-9, the compatibilizer is present in the sheath, whereas in Sample # 10, the compatibilizer is present in the core.

  Table 6 shows the processing conditions used to produce nonwovens from the bicomponent filament samples shown in Table 5. Samples were made on a Reicofil 4 spunbond system with 6827 holes / meter with a hole diameter of 0.6 millimeters. The core and sheath components were melted and extruded separately and then combined together by a stack of distribution plates to make a core / sheath filament structure. Filaments were randomly deposited on a moving belt and then thermally bonded through a calender (roll mill) with two rolls, one of which was an engraving roll and the other a smooth roll. It was.

  Table 7 shows the mechanical properties of Table 5 nonwoven samples after 4 and 8 weeks of production.

  From Table 7, it can be seen that the nonwovens having the bicomponent filaments disclosed herein exhibit an improvement in abrasion resistance without significantly adversely affecting the tensile properties. Also, from Tables 7 and 8, no significant differences in tensile properties and wear resistance are observed after 4 and 8 weeks of aging.

  Table 8 shows the fuzz level as a measure of the abrasion resistance of the nonwoven fabric. A lower fuzz level indicates better wear resistance.

  From the data in Table 8, it can be seen that the samples of the present invention (Samples # 3-9) show an improvement in wear resistance over time.

  The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm”.

  All documents cited herein, including any cross-reference or related patents or applications, and any patent applications or patents for which this application claims priority or benefit, are expressly excluded or present. Unless otherwise limited, the entirety of which is incorporated herein by reference. Citation of any document is either prior art with respect to any invention disclosed and claimed herein, or is it alone or with any other reference (s) No admission is made to teach, suggest, or disclose any such invention in any combination. To the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of that term in a document incorporated by reference, the meaning or definition given to that term in this document shall apply. It shall be.

  While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is intended by the appended claims to cover all such changes and modifications that are within the scope of this invention.

Claims (13)

A bicomponent filament,
A first region comprising an ethylene-based polymer;
A second region comprising a propylene-based polymer;
A crystalline block composite comprising (1) a crystalline ethylene polymer, (2) a crystalline alpha-olefin polymer, and (3) a block copolymer having the crystalline ethylene block and the crystalline alpha-olefin block. The crystalline ethylene block is essentially the same composition as the crystalline ethylene-based polymer, and the crystalline alpha-olefin block is essentially the same as the crystalline alpha-olefin polymer. The same composition,
A bicomponent filament in which the compatibilizer is present in at least one of the first region or the second region.   The bicomponent filament according to claim 1, wherein the crystalline ethylene-based polymer has an ethylene content of greater than 90 mol%. The crystalline alpha - olefin-based polymer, units derived from 90 mole percent propylene and C ₄ -C ₁₀ alpha - having a comonomer selected from the group consisting of olefins, a two-component according to claim 1 filament. The ethylene-based polymer has a density of 0.920 to 0.965 g / cc and a melt index, I ₂ , as determined according to ASTM D1238 at 190 ° C. and 2.16 kg, I _2. Item 2. The bicomponent filament according to Item 1.   2. The companion according to claim 1, wherein the compatibilizer is present only in the first region in an amount of 1% to less than 50% by weight, based on the total weight of the polymer present in the first region. Ingredient filament.   The two-component of claim 1, wherein the compatibilizer is present only in the second region in an amount of 1 wt% to less than 50 wt%, based on the total weight of the polymer present in the second region. filament.   The first region and the second region in an amount of 1% to less than 50% by weight of the compatibilizer based on the total weight of the polymer present in the first region and the second region. The bicomponent filament of claim 1 present in.   The first region and the second region are arranged in the form of a sheath / core, tip trefoil, segmented cloth, side-by-side, conjugate, island-in-sea, or segmented pie. The bicomponent filament according to claim 1.   The bicomponent filament according to claim 1, wherein the first region is a sheath of the bicomponent filament and the second region is a core of the bicomponent filament.   10. The bicomponent filament according to claim 9, wherein the core to sheath weight ratio is 50:50 to 90:10. A method of producing a bicomponent filament, the method comprising:
Blending a composition comprising an ethylene-based polymer, a propylene-based polymer, and a compatibilizer, wherein the compatibilizer comprises (1) a crystalline ethylene-based polymer, (2) a crystalline alpha-olefin-based polymer, and ( 3) comprising a crystalline block composite having a block copolymer having a crystalline ethylene block and a crystalline alpha-olefin block, wherein the crystalline ethylene block is essentially the same composition as the crystalline ethylene-based polymer; Blending, wherein the crystalline alpha-olefin block is essentially the same composition as the crystalline alpha-olefin-based polymer;
Extruding the composition to form a bicomponent filament;
The bicomponent filament is
A first region comprising an ethylene-based polymer and a second region comprising a propylene-based polymer;
The method wherein the compatibilizer is present in at least one of the first region or the second region.   The nonwoven fabric formed from the bicomponent filament as described in any one of Claims 1-10. A method for producing a nonwoven fabric, wherein the method comprises:
Providing two or more bicomponent filaments, each bicomponent filament comprising:
A first region comprising an ethylene-based polymer;
A second region comprising a propylene-based polymer;
A crystalline block composite comprising (1) a crystalline ethylene polymer, (2) a crystalline alpha-olefin polymer, and (3) a block copolymer having the crystalline ethylene block and the crystalline alpha-olefin block. The crystalline ethylene block is essentially the same composition as the crystalline ethylene-based polymer, and the crystalline alpha-olefin block is essentially the same as the crystalline alpha-olefin polymer. The same composition,
Providing the compatibilizer is present in at least one of the first region or the second region;
Bonding the two or more bicomponent filaments together to form a nonwoven fabric.